CN109420512A - A kind of catalysis material and its preparation method and application based on phosphoric acid modification - Google Patents
A kind of catalysis material and its preparation method and application based on phosphoric acid modification Download PDFInfo
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- CN109420512A CN109420512A CN201710786909.8A CN201710786909A CN109420512A CN 109420512 A CN109420512 A CN 109420512A CN 201710786909 A CN201710786909 A CN 201710786909A CN 109420512 A CN109420512 A CN 109420512A
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- lafeo
- photochemical catalyst
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- phosphate anion
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 title abstract description 24
- 239000000463 material Substances 0.000 title abstract description 19
- 238000012986 modification Methods 0.000 title abstract description 14
- 238000006555 catalytic reaction Methods 0.000 title abstract description 11
- 230000004048 modification Effects 0.000 title abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 229910017771 LaFeO Inorganic materials 0.000 claims abstract description 35
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 34
- 239000010452 phosphate Substances 0.000 claims abstract description 34
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 32
- 238000006366 phosphorylation reaction Methods 0.000 claims abstract description 31
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 229910002321 LaFeO3 Inorganic materials 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 20
- -1 phosphate anion Chemical class 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 150000002603 lanthanum Chemical class 0.000 claims description 11
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000007836 KH2PO4 Substances 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 20
- 238000003786 synthesis reaction Methods 0.000 abstract description 16
- 230000026731 phosphorylation Effects 0.000 description 27
- 230000001699 photocatalysis Effects 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 238000007146 photocatalysis Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 238000004176 ammonification Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000002798 spectrophotometry method Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004178 biological nitrogen fixation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a kind of catalysis materials and its preparation method and application based on phosphoric acid modification.Photochemical catalyst is the LaFeO of phosphorylation3, wherein La3+Formation site as phosphate radical.Photochemical catalyst of the invention can be used in fixed nitrogen synthesis ammonia.
Description
Technical field
The invention belongs to artificial fixed nitrogen synthesize ammonia field, be related to it is a kind of based on phosphoric acid modification photochemical catalyst and its application,
Suitable for fields such as environment, the energy, materials.
Background technique
Biological nitrogen fixation is photosynthetic important chemical process to be only second in nature, but the fixed nitrogen total amount of nature cannot
Meets the needs of industrial or agricultural, therefore artificial fixed nitrogen provides important support for the survival and development of the mankind.The ammonia catalyzed and synthesized
It is not only the pillar of agricultural production, as the compound of non-carbon hydrogen-rich, ammonia is more considered following clean fuel.Compared with hydrogen,
Liquefied ammonia have higher energy density, while also it is safer, be easy store and be readily transported.
Nitrogen molecule is highly stable, and three key bond energy of nitrogen nitrogen is up to 945.37kJmol-1, in homonuclear diatomic molecule most
Greatly.Classical ammonia synthesis reaction needs to carry out (15~25MPa, 300~500 DEG C) under high temperature and pressure, not only consumes a large amount of energy
Source (the global generated energy for accounting for 2%), and GHG carbon dioxide of the number in terms of hundreds of millions tons is discharged, cause serious environment to be asked
Topic.And although the metal complex for simulating azotase can be realized the nitrogen activation under temperate condition, but its low efficiency, only
It is the 1/1000 of biological nitrogen-fixing efficiency, secondly, being also not easy to realize separation and recovery as homogeneous catalyst.
Compared with the metal complex of homogeneous catalysis, realize that fixed nitrogen reaction has more in a mild condition by photocatalysis
It is attractive.Photocatalysis fixed nitrogen is a kind of new catalysis technique for converting nitrogen to using luminous energy and semiconductor ammonia, however, such as
What further increases the service life of photo-generated carrier and improves photocatalysis nitrogen-fixing efficiency, is to have important Science and Technology to be solved to ask
Topic.Current deficiency is mainly reflected in: 1. need the position of energy band of catalysis material, improve utilization rate and photoproduction to light
The transport efficiency of carrier makes the surface electronic/hole for moving to surface have stronger oxidation-reduction quality;2. needing to construct light
The N on catalysis material surface2Site is activated, and improves its stability;3.N2The generation of reduzate needs to cooperate H+Ion or proton
Transfer, general photocatalytic system then Selection utilization hole sacrifice agent provide, however from application angle for, add sacrifice agent or
Solvent increases reaction cost and brings the new problems such as " three wastes " discharge and improvement.
Summary of the invention
In view of the above-mentioned problems, the purpose of the present invention is to provide the catalyst and structure of a kind of high activity photocatalytic synthesis ammonification
Build mild, the photocatalytic synthesis ammonification material system of low energy consumption and application.
In a first aspect, the present invention provides a kind of photochemical catalyst, the photochemical catalyst is the LaFeO of phosphorylation3, wherein La3+
Formation site as phosphate radical.
Photochemical catalyst of the invention can be used in fixed nitrogen synthesis ammonia, specifically, the present invention is synthesized for photocatalysis fixed nitrogen
The differential responses course of this specific catalytic process of ammonia, comprising: N2The activation of molecule, the separation of photo-generated carrier, hydrone
Dissociation and NH3Generation, design photochemical catalyst based on surface modification and its catalysis and synthesis ammono-system.The present invention is logical first
Surface phosphoric acid is crossed, more active sites is constructed in photocatalyst surface, is advantageously implemented the activation of nitrogen;Secondly, passing through table
Face phosphorylation realizes that light excites the dissociation of lower hydrone, promotes N2Hydrogenation synthesis ammonia.After surface phosphoric acid, the hydrogen bond and iron of phosphoric acid
The iron ion on sour lanthanum surface forms double activated site, plays the role of collaboration and promotes nitrogen activation.
More preferably, the photochemical catalyst is powder, it is preferable that partial size is 50~500nm.
Second aspect, the present invention provide the preparation method of above-mentioned photochemical catalyst, will be adsorbed with the LaFeO of phosphate anion3
It is calcined 1~10 hour at 150~500 DEG C, obtains the photochemical catalyst.
Photochemical catalyst preparation of the invention is simple, does not generate any pollution during the preparation process, be a kind of sustainability compared with
High environmentally protective synthesis technology.
More preferably, the LaFeO for being adsorbed with phosphate anion3It is by LaFeO3It is soaked in containing the molten of phosphate anion
It is obtained in liquid.
More preferably, the solution containing phosphate anion is selected from H3PO4、NaH2PO4And KH2PO4At least one of.
More preferably, the concentration of phosphate anion is 0.01~0.5M in the solution containing phosphate anion, preferably
0.01M~0.2M.
More preferably, LaFeO3It is prepared via a method which: lanthanum salt, molysite and citric acid is uniformly mixed in water, be added
It is between 8~13 and to stir that aqueous slkali, which adjusts pH value, is precipitated;It will calcine, obtain after the cleaning of obtained precipitating
LaFeO3。
More preferably, lanthanum salt and/or the concentration of molysite are as follows: between 0.01M~0.2M.
More preferably, the concentration of citric acid are as follows: between 0.01M~0.2M.
More preferably, the concentration of aqueous slkali is between 0.2M~0.5M.
More preferably, calcination temperature is between 200~800 DEG C.
The third aspect, the present invention provide a kind of green syt ammonia process, under light source irradiation, are passed through N2/H2O mixed gas,
Using above-mentioned photochemical catalyst, so that the H being passed through2O/N2It reacts to form NH3。
More preferably, the N2/H2N in O mixed gas2/H2The molar ratio of O is (10~100): 1.Preferably, the N2/
H2The flow velocity of O mixed gas is 60~100mL/ minutes.
More preferably, the irradiation power of the light source is 10~500W.
The invention has the following advantages that
1, the present invention synthesizes the phosphorylation LaFeO with photocatalysis fixed nitrogen function3, avoid using noble metal;
2, the present invention avoids the addition of sacrifice agent during synthesizing ammonia;
3, catalyst of the invention has visible light-responded ability, and photocatalysis fixed nitrogen can be made to complete under visible light conditions, made
It is with broader practice prospect;
4, the present invention does not generate any pollution in preparation and the realization photocatalysis fixed nitrogen of catalyst, is that a kind of sustainability is higher
Environmentally protective synthesis technology.
Detailed description of the invention
Fig. 1 is the LaFeO that in an embodiment of the present invention prepared by hydro-thermal3XRD diffracting spectrum;
Fig. 2 is the LaFeO that in an embodiment of the present invention prepared by hydro-thermal3Infared spectrum;
Fig. 3 is the LaFeO that in an embodiment of the present invention prepared by hydro-thermal3Ultraviolet-visible absorption spectroscopy;
Fig. 4 is the LaFeO that in an embodiment of the present invention prepared by hydro-thermal3Transmission electron microscope;
Fig. 5 is phosphorylation LaFeO in an embodiment of the present invention3Synthesize yield-time diagram of ammonia;
Fig. 6 is that whether there is or not the synthesis ammonia efficiency comparative of phosphoric acid decorative material figures;
Fig. 7 is phosphorylation LaFeO in another embodiment of the present invention3Synthesize yield-time diagram of ammonia;
Fig. 8 is phosphorylation LaFeO in a further embodiment of this invention3Calcination temperature is to ammonia yield impact comparison diagram;
Fig. 9 is phosphorylation LaFeO in a further embodiment of this invention3Photoluminescence spectrum.
Specific embodiment
The present invention is further illustrated by following embodiments, it should be appreciated that following embodiments are merely to illustrate the present invention,
It is not intended to limit the present invention.
An embodiment of the present invention provides a kind of LaFeO of phosphoric acid modification3Material.Wherein, LaFeO3For perovskite knot
Structure.In LaFeO3Surface contain phosphate radical.La3+Formation site as phosphate radical.LaFeO3Molar ratio with phosphate radical can
For 1:(0.01~0.1).
The LaFeO of phosphoric acid modification3Material can exist with powder.The partial size of powder can be 50~500nm.
The LaFeO of phosphoric acid modification3Material has visible light-responded ability, and forbidden bandwidth is in 1.9eV or so.
The LaFeO of phosphoric acid modification3Material can be used as photochemical catalyst and synthesize ammonia for fixed nitrogen.
Then, illustrate the LaFeO of phosphoric acid modification3The preparation method of material.
In an embodiment of the present invention, phosphate anion (PO will be adsorbed with4 3-) LaFeO3It is heat-treated, obtains phosphorus
The LaFeO of acid modification3Material.Heat treatment temperature can be 150~500 DEG C.Preferably, heat treatment temperature is 150~300 DEG C.It should
Heat treatment temperature, which is more advantageous to, avoids powder that secondary agglomeration occurs.Heat treatment time can be 1~10 hour, and preferably 2~8 is small
When.After heat treatment, the phosphate radical with acidic character preferentially with alkalinity La3+It is coordinated, to be anchored on LaFeO3Surface.
Furthermore the heat treatment loaded favourable of phosphoric acid is in generating defect in catalyst surface, to promote the absorption of light.
In LaFeO3The method of middle absorption phosphate anion is unlimited, such as can be LaFeO3It is impregnated in containing phosphate radical
A period of time in the solution of ion is then demultiplex out, cleans and obtain.
Solution containing phosphate anion can be phosphoric acid and/or phosphate, including but not limited to H3PO4、NaH2PO4Or
KH2PO4At least one of.The concentration of phosphate anion can be according in LaFeO in solution containing phosphate anion3It repairs on surface
The number of the amount of the phosphate radical of decorations selects.For example, if you need to modify compared with multi-phosphate, then can make the concentration of phosphate anion compared with
Greatly.In one example, the concentration of phosphate anion is 0.01M~0.5M, preferably 0.01M in the solution containing phosphate anion
~0.2M, more preferably 0.01M~0.1M.Dip time also can be according in LaFeO3The number of the amount of the phosphate radical of surface modification
To select.For example, then dip time can be made longer if you need to modify compared with multi-phosphate.In one example, dip time be 0.5~
24 hours.In addition, dipping process can also stir.
Used LaFeO3It is purchased from commercial or voluntarily prepares.In one example, it is prepared via a method which LaFeO3。
Lanthanum salt is uniformly mixed in aqueous solution with molysite, citric acid and aqueous slkali is added and is stirred.Obtained precipitating is cleaned laggard
Row calcining.
Lanthanum salt may be, for example, at least one of lanthanum nitrate, lanthanum chloride, lanthanum acetate.
Molysite may be, for example, at least one of ferric nitrate, iron chloride, ferric acetate, ferric acetyl acetonade.
Lanthanum salt and molysite are preferably equimolar ratio.Lanthanum salt, the molar concentration of molysite can are as follows: between 0.01M~0.2M.
Citric acid concentration can are as follows: between 0.01M~0.2M.Lanthanum salt and the molar ratio of citric acid can be 1:(0.1~10).
Aqueous slkali can be at least one of NaOH aqueous solution, KOH aqueous solution, sodium bicarbonate.The concentration of aqueous slkali can
Between 0.2M~0.5M.The pH value of entire reaction system can be between 8~13 preferably 8.5~10.
In addition, it should be understood that the addition sequence of lanthanum salt, molysite, citric acid, aqueous slkali be not limited to it is above-mentioned, such as can also be with
It is first to mix lanthanum salt, molysite and citric acid, adds aqueous slkali.
The calcination temperature of precipitating can be 200~800 DEG C, preferably 300~800 DEG C, more preferably 400~600 DEG C.
The synthesis of ammonia
Catalyzing and synthesizing ammono-system includes: phosphoric acid modification catalysis material, nitrogen gas and water and light source.Specifically, being modified by phosphoric acid
LaFeO3Material (photochemical catalyst) utilizes H under illumination condition2O is by N2It is reduced to NH3.Hereinafter, illustrating photo catalytic reduction N2And
Generate NH3Operating method a specific example.
(1) photochemical catalyst is added in the reactor, is dispersed in reactor.
(2) N is passed through into reactor2/H2O mixed gas.The gas flow rate being passed through in reactor can be 60~100mL/
min。N2/H2N in O mixed gas2/H2The molar ratio of O can be (10~100): 1.The molar ratio of photochemical catalyst and mixed gas can
For 1:(10~100).In one example, the quality of photochemical catalyst can be 0.1~0.5g.
(3) with the photochemical catalyst in light source irradiation reactor, it is made to react with the gas being passed through.Light source can be artificial
Light source or lamp.As long as in addition, light source be capable of providing excitation photochemical catalyst generate photo-generate electron-hole pairs light source,
Such as ultraviolet-visible light.Irradiation power can be 50~500W.The reaction system to temperature without particular/special requirement, can be very wide
It carries out, such as can simply react at room temperature in temperature range.Reaction time can be 0.5~48 hour, preferably 0.5~4
Hour.
(4) product obtained is acid or neutral solution (such as dilute acid soln) is collected, and (receives according to national standard method
Family name's reagent spectrophotometry) carry out ammonia density detection.
The result shows that the LaFeO that phosphoric acid of the invention is modified3When material synthesizes ammonia for fixed nitrogen as photochemical catalyst,
Yield can be 50~300 μm of ol/gh.
Simple, cheap and easy to get, the visible light utilization efficiency of material component of the present invention is high, while being suitble to magnanimity preparation, has application
Prospect.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1
Phosphorylation LaFeO with photocatalysis fixed nitrogen function3The preparation method is as follows:
(1) citric acid for weighing the ferric nitrate of 1.5mmol, 1.5mmol lanthanum nitrate and 3mmol is dissolved in 35ml deionized water,
Uniform stirring is realized by magnetic stirring apparatus at room temperature, until it is completely dissolved;
(2) NaOH solution of 2M is configured, and pH value of above-mentioned solution is adjusted to 9 or so with it;
(3) powder of precipitating is placed in Muffle furnace, at 650 DEG C and keeps the temperature 3h, finally cools down, obtain powder sample;
(4) powder sample is impregnated in the phosphoric acid of 0.2M and is stirred 1 hour;
(5) 2 hours are kept the temperature at 300 DEG C after filtering out powder, secondary heat treatment is carried out, obtains phosphorylation LaFeO3。
To phosphorylation LaFeO obtained by embodiment 13It is characterized.Through XRD characterization, gained phosphorylation LaFeO3Photocatalysis
Agent is really perovskite structure and without obvious miscellaneous phase, sees Fig. 1;It is characterized through FTIR spectrum, shows obtained phosphorylation
LaFeO3Photocatalyst surface contains phosphate radical, sees Fig. 2;Show obtained phosphorylation by ultraviolet-visible absorption spectroscopy
LaFeO3There are visible light-responded ability, forbidden bandwidth is shown in Fig. 3 in 1.9eV or so.It is observed under its transmission electron microscope
The pattern arrived is as shown in figure 4, phosphorylation LaFeO3For spherical shape, granular size is 300nm or so.
Embodiment 2
To phosphorylation LaFeO obtained in embodiment 13Carry out synthesis ammonia characterization
Experimental procedure include: 1. by photochemical catalyst 0.1g obtained in embodiment 1 dispersion in the reactor.2. leading into reactor
Enter N2/H2O mixed gas, gas flow rate are 150mL/ minutes, N2/H2The molar ratio of O is 100:1, and the gas gross being passed through is
9L.3. bringing it about light-catalyzed reaction using the photochemical catalyst in 500W xenon lamp irradiation reactor.4. molten with 0.2mmol acidity
Liquid is as NH3Absorbing liquid, according to Berthelot spectrophotometry to NH3Concentration Testing.Fig. 5 show phosphorylation LaFeO3It closes
Yield-time diagram of ammonification.From fig. 5, it can be seen that ammonia yield show it is linearly increasing, yield be 100 μm of ol/gh.
Comparative example 1
Non- phosphorylation LaFeO3Preparation method, the method in reference implementation example 1 removes (4), (5).
Comparative example 2
The obtained non-phosphorylation LaFeO into comparative example 13Synthesis ammonia characterization is carried out, except photochemical catalyst is unphosphorylated
LaFeO3In addition, remaining method is consistent in embodiment 2.Whether there is or not synthesis ammonia efficiency comparative such as Fig. 6 institutes of phosphoric acid decorative material
Show.From fig. 6, it can be seen that by the resulting phosphorylation LaFeO of embodiment 13Ammonia yield be 100 μm of ol/gh, and non-phosphorylation
LaFeO3Yield be 32 μm of ol/gh, it is seen that the LaFeO of phosphorylation3It is non-phosphorylation LaFeO3Ammonia yield 3 times of left sides
It is right.
Embodiment 3
Phosphorylation LaFeO with photocatalysis fixed nitrogen function3The preparation method is as follows:
(1) citric acid for weighing the ferric acetyl acetonade of 1.5mmol, 1.5mmol lanthanum acetate and 3mmol is dissolved in 40ml deionized water
In, uniform stirring is realized by magnetic stirring apparatus at room temperature, until it is completely dissolved;
(2) KOH solution of 2M is configured, and pH value of above-mentioned solution is adjusted to 8 or so with it;
(3) powder of precipitating is placed in Muffle furnace, at 650 DEG C and keeps the temperature 3h, finally cools down, obtain powder sample;
(4) powder sample is impregnated in the phosphoric acid of 0.2M and is stirred 3 hours;
(5) 2 hours are kept the temperature at 500 DEG C after filtering out powder, secondary heat treatment is carried out, obtains phosphorylation LaFeO3。
Embodiment 4
To phosphorylation LaFeO obtained in embodiment 33Carry out synthesis ammonia characterization
Experimental procedure include: 1. by photochemical catalyst 0.1g obtained in embodiment 1 dispersion in the reactor.2. leading into reactor
Enter N2/H2O mixed gas, gas flow rate are 150mL/ minutes, N2/H2The molar ratio of O is 100:1, and the gas gross being passed through is
9L.3. bringing it about light-catalyzed reaction using the photochemical catalyst in 500W xenon lamp irradiation reactor.4. molten with 0.2mmol acidity
Liquid is as NH3Absorbing liquid, according to Berthelot spectrophotometry to NH3Concentration Testing.Fig. 7 show phosphorylation LaFeO3It closes
Yield-time diagram of ammonification.From figure 7 it can be seen that ammonia yield shows linearly increasing, yield is 50 micromoles, and yield is
125μmol/g·h。
Embodiment 5
Phosphorylation LaFeO with photocatalysis fixed nitrogen function3The preparation method is as follows:
(1) citric acid for weighing the ferric acetyl acetonade of 1.5mmol, 1.5mmol lanthanum acetate and 3mmol is dissolved in 40ml deionized water
In, uniform stirring is realized by magnetic stirring apparatus at room temperature, until it is completely dissolved;
(2) KOH solution of 2M is configured, and pH value of above-mentioned solution is adjusted to 8 or so with it;
(3) powder of precipitating is placed in Muffle furnace, at 650 DEG C and keeps the temperature 3h, finally cools down, obtain powder sample;
(4) powder sample is impregnated in the phosphoric acid of 0.2M and is stirred 3 hours;
(5) 2 hours are kept the temperature at 150 DEG C after filtering out powder, secondary heat treatment is carried out, obtains phosphorylation LaFeO3。
Embodiment 6
To phosphorylation LaFeO obtained in embodiment 53Carry out synthesis ammonia characterization
Experimental procedure include: 1. by photochemical catalyst 0.1g obtained in embodiment 1 dispersion in the reactor.2. leading into reactor
Enter N2/H2O mixed gas, gas flow rate are 150mL/ minutes, N2/H2The molar ratio of O is 100:1, and the gas gross being passed through is
9L.3. bringing it about light-catalyzed reaction using the photochemical catalyst in 500W xenon lamp irradiation reactor.4. molten with 0.2mmol acidity
Liquid is as NH3Absorbing liquid, according to Berthelot spectrophotometry to NH3Concentration Testing.Ammonia yield is 280 as can be seen from Figure 8
μm ol/gh, result in comparative example 4 essentially consist in it is found that the calcination temperature of phosphoric acid plays great influence to ammonia yield
Low temperature calcination is more advantageous to the reunion for preventing nano particle.From fig. 9, it can be seen that the LaFeO after load phosphoric acid3Luminescence generated by light
Spectral intensity weakens, and shows that phosphoric acid load promotes the separation of carrier, improves photocatalysis efficiency.
Claims (10)
1. a kind of photochemical catalyst, which is characterized in that the photochemical catalyst is the LaFeO of phosphorylation3, wherein La3+As phosphate radical
Formation site.
2. photochemical catalyst according to claim 1, which is characterized in that the photochemical catalyst is powder, it is preferable that partial size is
50~500 nm.
3. a kind of preparation method of photochemical catalyst of any of claims 1 or 2, which is characterized in that phosphate anion will be adsorbed with
LaFeO3It is calcined 1~10 hour at 150~500 DEG C, obtains the photochemical catalyst.
4. preparation method according to claim 3, which is characterized in that the LaFeO for being adsorbed with phosphate anion3Being will
LaFeO3It is soaked in the solution containing phosphate anion and obtains.
5. the preparation method according to claim 4, which is characterized in that the solution containing phosphate anion is selected from
H3PO4、NaH2PO4And KH2PO4At least one of;Preferably, phosphate anion in the solution containing phosphate anion
Concentration be 0.01~0.5M.
6. preparation method according to any one of claim 3 to 5, which is characterized in that LaFeO3It makes by the following method
It is standby: lanthanum salt, molysite and citric acid uniformly to be mixed in water, it is between 8~13 and to stir that aqueous slkali, which is added, and adjusts pH value, is obtained
Precipitating;Obtained precipitating is calcined, LaFeO is obtained3。
7. preparation method according to claim 6, which is characterized in that the concentration of lanthanum salt and/or molysite are as follows: 0.01M~
Between 0.2M;The concentration of citric acid are as follows: between 0.01M~0.2M;The concentration of aqueous slkali is between 0.2M~0.5M;Calcining temperature
Degree is between 200~800 DEG C.
8. a kind of method for synthesizing ammonia, which is characterized in that under light source irradiation, be passed through N2/H2O mixed gas, utilizes claim
Photochemical catalyst described in 1 or 2, so that the H being passed through2O and N2It reacts and generates NH3。
9. according to the method described in claim 8, it is characterized in that, the N2/H2N in O mixed gas2/H2The molar ratio of O is
(10~100): 1, the N2/H2The flow velocity of O mixed gas is 60~100 mL/ minutes;Preferably, the irradiation function of the light source
Rate is 10~500 W.
10. one kind catalyzes and synthesizes ammono-system, which is characterized in that including photochemical catalyst of any of claims 1 or 2, nitrogen gas and water and
Light source.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110227474A (en) * | 2019-07-04 | 2019-09-13 | 中国科学技术大学 | A kind of LaCoO with Lacking oxygen3The preparation method and application of nano material |
CN110963504A (en) * | 2019-12-06 | 2020-04-07 | 深圳市中科墨磷科技有限公司 | Application of black phosphorus material in photoelectric nitrogen fixation |
CN113373307A (en) * | 2021-04-28 | 2021-09-10 | 上海师范大学 | Method for carrying out photocatalytic metal dissolution by using phosphate radical modified photocatalyst |
CN113856611A (en) * | 2021-09-28 | 2021-12-31 | 淮阴师范学院 | Magnetic dodecahedron lanthanum ferrite adsorbent and preparation method thereof |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3992328A (en) * | 1974-10-30 | 1976-11-16 | The Lummus Company | Process for the preparation of ammonia synthesis catalyst and catalyst prepared by the process |
CN1670088A (en) * | 2004-03-17 | 2005-09-21 | 住友化学株式会社 | Coating composition of photocatalyst |
CN1986052A (en) * | 2006-12-29 | 2007-06-27 | 南开大学 | Catalyst for decomposing hydrogen phosphide to prepare simple substance phosphorus and its preparation and application |
CN101676026A (en) * | 2008-09-18 | 2010-03-24 | 中国石油天然气股份有限公司 | Iron ammonia synthesis catalyst and preparation method |
JP2011050855A (en) * | 2009-09-02 | 2011-03-17 | Babcock Hitachi Kk | Exhaust gas purifying apparatus |
KR101392828B1 (en) * | 2012-12-04 | 2014-05-08 | 한국에너지기술연구원 | Ammonia fabrication method |
KR101470929B1 (en) * | 2013-09-11 | 2014-12-09 | 한국에너지기술연구원 | Electrochemical Module for Ammonia Synthesis Using Catalytic Electrode of Metal Nitride, Fabrication Method thereof and Ammonia Synthesis Method using the same |
CN106861621A (en) * | 2017-03-24 | 2017-06-20 | 华纺股份有限公司 | A kind of La2O3/Fe2O3The preparation technology of carbon fibre material |
CN106881096A (en) * | 2017-03-31 | 2017-06-23 | 武汉理工大学 | Mesoporous LaFeO3The preparation method of perovskite type composite oxide catalyst material |
CN106902729A (en) * | 2017-03-31 | 2017-06-30 | 华中师范大学 | A kind of Zr La metal composite oxides, preparation and its control body eutrophication remove phosphatic application |
CN107029777A (en) * | 2017-05-26 | 2017-08-11 | 长沙学院 | Composite visible light catalyst and its preparation method and application |
CN107376926A (en) * | 2017-08-18 | 2017-11-24 | 中国科学院过程工程研究所 | A kind of Ca-Ti ore type ozone decomposition catalyst and its preparation method and application |
CN107754765A (en) * | 2017-11-23 | 2018-03-06 | 南昌航空大学 | A kind of La doped metal-organic framework materials and its preparation method and application |
-
2017
- 2017-09-04 CN CN201710786909.8A patent/CN109420512A/en active Pending
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3992328A (en) * | 1974-10-30 | 1976-11-16 | The Lummus Company | Process for the preparation of ammonia synthesis catalyst and catalyst prepared by the process |
CN1670088A (en) * | 2004-03-17 | 2005-09-21 | 住友化学株式会社 | Coating composition of photocatalyst |
CN1986052A (en) * | 2006-12-29 | 2007-06-27 | 南开大学 | Catalyst for decomposing hydrogen phosphide to prepare simple substance phosphorus and its preparation and application |
CN101676026A (en) * | 2008-09-18 | 2010-03-24 | 中国石油天然气股份有限公司 | Iron ammonia synthesis catalyst and preparation method |
JP2011050855A (en) * | 2009-09-02 | 2011-03-17 | Babcock Hitachi Kk | Exhaust gas purifying apparatus |
KR101392828B1 (en) * | 2012-12-04 | 2014-05-08 | 한국에너지기술연구원 | Ammonia fabrication method |
KR101470929B1 (en) * | 2013-09-11 | 2014-12-09 | 한국에너지기술연구원 | Electrochemical Module for Ammonia Synthesis Using Catalytic Electrode of Metal Nitride, Fabrication Method thereof and Ammonia Synthesis Method using the same |
CN106861621A (en) * | 2017-03-24 | 2017-06-20 | 华纺股份有限公司 | A kind of La2O3/Fe2O3The preparation technology of carbon fibre material |
CN106881096A (en) * | 2017-03-31 | 2017-06-23 | 武汉理工大学 | Mesoporous LaFeO3The preparation method of perovskite type composite oxide catalyst material |
CN106902729A (en) * | 2017-03-31 | 2017-06-30 | 华中师范大学 | A kind of Zr La metal composite oxides, preparation and its control body eutrophication remove phosphatic application |
CN107029777A (en) * | 2017-05-26 | 2017-08-11 | 长沙学院 | Composite visible light catalyst and its preparation method and application |
CN107376926A (en) * | 2017-08-18 | 2017-11-24 | 中国科学院过程工程研究所 | A kind of Ca-Ti ore type ozone decomposition catalyst and its preparation method and application |
CN107754765A (en) * | 2017-11-23 | 2018-03-06 | 南昌航空大学 | A kind of La doped metal-organic framework materials and its preparation method and application |
Non-Patent Citations (3)
Title |
---|
GUIGAO LIU ET AL: "Nature-Inspired Environmental "Phosphorylation" Boosts Photocatalytic H2 Production over Carbon Nitride Nanosheets under Visible-Light Irradiation", 《ANGEWANDTE CHEMIE》 * |
HAJIME MIYAMA ET AL: "Heterogeneous photocatalytic synthesis of ammonia from water and nitrogen", 《CHEMICAL PHYSICS LETTERS》 * |
K.M. PARIDA ET AL: "Fabrication of nanocrystalline LaFeO3: An efficient solegel auto-combustion assisted visible light responsive photocatalyst for water decomposition", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110227474A (en) * | 2019-07-04 | 2019-09-13 | 中国科学技术大学 | A kind of LaCoO with Lacking oxygen3The preparation method and application of nano material |
CN110963504A (en) * | 2019-12-06 | 2020-04-07 | 深圳市中科墨磷科技有限公司 | Application of black phosphorus material in photoelectric nitrogen fixation |
CN110963504B (en) * | 2019-12-06 | 2022-11-11 | 深圳市中科墨磷科技有限公司 | Application of black phosphorus material in photoelectric nitrogen fixation |
CN113373307A (en) * | 2021-04-28 | 2021-09-10 | 上海师范大学 | Method for carrying out photocatalytic metal dissolution by using phosphate radical modified photocatalyst |
CN113856611A (en) * | 2021-09-28 | 2021-12-31 | 淮阴师范学院 | Magnetic dodecahedron lanthanum ferrite adsorbent and preparation method thereof |
CN113856611B (en) * | 2021-09-28 | 2023-07-11 | 淮阴师范学院 | Magnetic dodecahedron lanthanum ferrite adsorbent and preparation method thereof |
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